Hydrocarbon conversion with a multimetallic catalytic composite

ABSTRACT

Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with a trimetallic acidic catalytic composite comprising a combination of catalytically effective amounts of a platinum group component, a Group IVA component, a lanthanide component and a halogen component with a porous carrier material. The platinum group component, Group IVA metallic component, and halogen component are present in the trimetallic catalyst in amounts respectively, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % Group IVA metal and about 0.1 to about 3.5 wt. % halogen. The lanthanide component is present in amounts corresponding to an atomic ratio of lanthanide element to platinum group metal of about 0.1:1 to about 1.25:1. Moreover, these metallic components are uniformly dispersed throughout the porous carrier material in carefully controlled oxidation states such that substantially all of the platinum group metal is present therein in the elemental metallic state while substantially all of the Group IVA metallic component and of the lanthanide component are present therein in oxidation states above that of the corresponding metals. A specific example of the type of hydrocarbon conversion process disclosed is a process for the catalytic reforming of a low-octane gasoline fraction wherein the gasoline fraction and hydrogen stream are contacted with the novel trimetallic catalyst disclosed herein at reforming conditions.

United States Patent [1 1 Antos Oct. 28, 1975 HYDROCARBON CONVERSIONWITH A MULTIMETALLIC CATALYTIC COMPOSITE [75] Inventor: George J. Antos,Arlington Heights,

[73] Assignee: Universal Oil Products Company, Des Plaines, Ill.

[22] Filed: Dec. 6, 1973 [21] Appl. No.: 422,464

[52] U.S. Cl. 208/139; 208/111; 208/112;

260/683.68; 260/668; 252/441 [51] Int. Cl. ..C10G 13/10; C10G 35/08;C07C 5/30; B01J 27/06 [58] Field of Search 208/138, 139,111, 112;260/683.68, 668 A; 252/441 [56] References Cited UNITED STATES PATENTS2,976,232 3/1961 Porter et al 208/138 3,223,617 12/1965 Mazink 208/1383,632,502 1/1972 Kittrell 208/111 3,686,340 8/1972 Patrick et a1.208/138 3,700,745 10/1972 Kovach et al. 208/112 3,702,293 11/1972 Hayeset a1. 208/139 3,770,616 ll/1973 Kominami ct a1. 208/138 3,776,86012/1973 Rai 208/138 Primary Examin erDelbert E. Gantz AssistantExaminer.lames W. Hellwege Attorney, Agent, or FirmJames R. Hoatson,Jr.; Thomas K. McBride; William H. Page, 11

57 ABSTRACT Hydrocarbons are converted by contacting them at hydrocarbon"conversion conditions with a trimetallic acidic catalytic compositecomprising a combination of catalytically effective amounts of aplatinum group component, a Group IVA component, a lanthanide componentand a halogen component with a porous carrier material. The platinumgroup component, Group IVA metallic component, and halogen component arepresent in the trimetallic catalyst in amounts respectively, calculatedon an elemental basis, corresponding to about 0.01 to about 2 wt.platinum group metal, about 0.01 to about 5 wt. 7: Group IVA metal andabout 0.1 to about 3.5 wt. halogen. The lanthanide component is presentin amounts corresponding to an atomic ratio of lanthanide element toplatinum group metal of about 0.1:1 to about 1.25:1. Moreover, thesemetallic components are uniformly dispersed throughout the porouscarrier material in carefully controlled oxidation states such thatsubstantially all of the platinum group metal is present therein in theelemental metallic state while substantially all of the Group IVAmetallic component and of the lanthanide component are present thereinin oxidation states above that of the corresponding metals. A specificexample of the type of hydrocarbon conversion process disclosed is aprocess for the catalytic reforming of a low-octane gasoline fractionwherein the gasoline fraction and hydrogen stream are contacted with thenovel trimetallic catalyst disclosed herein at reforming conditions.

21 Claims, No Drawings I-IYDROCARBON CONVERSION WITH A MULTIMETALLICCATALYTIC COMPOSITE The subject of the present invention is a novelacidic trimetallic catalytic composite which has exceptional activityand resistance to deactivation when employed in a hydrocarbon conversionprocess that requires a catalyst having both ahydrogenation-dehydrogenation fuction and a selective cracking function.More precisely, the present invention involves a novel dual-functionacidic trimetallic catalytic composite which, quite surprisingly,enables substantial improvements in hydrocarbon conversion processesthat have traditionally used a dual-function catalyst. In anotheraspect, the present invention comprehends the improved processes thatare produced by the use of a catalytic composite comprising acombination of catalytically effective amounts of a platinum groupcomponent, a lanthanide component, a Group IVA metallic component and ahalogen component with a porous carrier material; specifically, animproved reforming process which utilizes the subject catalyst toimprove activity, selectivity, and stability characteristics.

Composites having a hydrogenation-dehydrogenation function and acracking function are widely used today as catalysts in many industries,such as the petroleum and petrochemical industry, to accelerate a widespectrum of hydrocarbon conversion reactions. Generally, the crackingfunction is thought to be associated with an acid-acting material of theporous, adsorptive, refractory oxide type which is typically utilized asthe support or carrier for a heavy metal component such as thetransition metals or compounds of the transition metals of Groups Vthrough VIII of the Periodic Table to which are generally attributed thehydrogenationdehydrogenation function.

These catalytic composites are used to accelerate a wide variety ofhydrocarbon conversion reactions such as hydrocracking, isomerization,dehydrogenation, hydrogenation, desulfurization, cyclization,alkylation, polymerization, cracking, hydroisomerization, etc. In manycases, the commercial applications of these catalysts are in processeswhere more than one of these reactions are proceeding simultaneously. Anexample of this type of process is reforming wherein a hydrocarbon feedstream containing paraffins and naphthenes is subjected to conditionswhich promote dehydrogenation of naphthenes to aromatics,dehydrocyclization of paraffins to aromatics, isomerization of paraffinsand naphthenes, hydrocracking of naphthenes and paraffins and the likereactions, to produce an octane-rich or aromatic-rich product stream.Another example is a hydrocracking process wherein catalysts of thistype are utilized to effect selective hydrogenation and cracking of highmolecular weight unsaturated materials, selective hydrocracking of highmolecular weight materials, and other like reactions, to produce agenerally lower boiling, more valuable output stream. Yet anotherexample is a hydroisomerization process wherein a hydrocarbon fractionwhich is relatively rich in straight-chain paraffins is contacted with adualfunction catalyst in the presence of hydrogen to produce an outputstream rich in isoparaffins.

Regardless of the reaction involved or the particular process involved,it is of critical importance that the dual-function catalyst exhibit notonly the capability to initially perform its specified functions, butalso that it has the capability to perform them satisfactorily forprolonged periods of time. The analytical terms used in the art tomeasure how well a particular catalyst performs its intended functionsin a particular hydrocarbon reaction environment are activity,selectivity, and stability. And for purposes of discussion here, theseterms are conveniently defined for a given charge stock as follows: (1)activity is a measure of the catalysts ability to convert hydrocarbonreactants into products at a specified severity level where severitylevel means the conditions used that is, the temperature, pressure,contact time, and presence of diluents such as H (2) selectivity refersto the amount of desired product or products obtained relative to theamount of reactants charged or converted; (3) stability refers to therate of change with time of activity and selectivity parametersobviously, the smaller rate implying the more stable catalyst. In areforming process, for example, activity commonly refers to the amountof conversion that takes place for a given charge stock at a specifiedseverity level and is typically measured by octane number of the C5+product stream; selectivity refers to the amount of C yield relative tothe amount of the charge that is obtained at the particular activity orseverity level; and stability is typically equated to the rate of changewith time of activity, as measured by octane number of C product, and ofselectivity, as measured by C yield. Actually, this last statement isnot strictly correct because generally a continuous reforming process isrun to produce a constant octane C product with severity level beingcontinuously adjusted to attain this result; and, furthermore, theseverity level is for this process usually varied by adjusting theconversion temperature in the reaction zone so that, in point of fact,the rate of change of activity finds response in the rate of change ofconversion temperature and changes in this last parameter arecustomarily taken as indicative of activity stability.

As is well known to those skilled in the art, the principal cause ofobserved deactivation or instability of a dual-function catalyst when itis used in a hydrocarbon conversion reaction is associated with the factthat coke forms on the surface of the catalyst during the course of thereaction. More specifically, in these hydrocarbon conversion processes,the conditions utilized typically result in the formation of heavy, highmolecular weight, black, solid or semi-solid, carbonaceous materialwhich coats the surface of the catalyst and reduces its activity byshielding its active sites from the reactants. In other words theperformance of this dual-function catalyst is sensitive to the presenceof carbonaceous deposits on the surface of the catalyst. Accordingly,the major problem facing workers in this area of the art is thedevelopment of more active and selective catalytic composites that arenot as sensitive to the presence of these carbonaceous materials and/orhave the capability to suppress the rate of the formation of thesecarbonaceous materials on the catalyst. Viewed in terms of performanceparameters, the problem is to develop a dual-function catalyst havingsuperior activity, selectivity, and stability. In particular, for areforming process the problem is typically expressed in terms ofshifting and stabilizing the C yield-octane relationship C yield beingrepresentative of selectivity and octane being proportional to activity.

I have now found a dual-function trimetallic acidic catalytic compositewhich possesses improved activity, selectivity, and stabilitycharacteristics when it is employed in a process for the conversion ofhydrocarbons of the type which have heretofore utilized dual-functionacidic catalytic composites such as processes for isomerization,hydroisomerization, dehydrogenation, desulfurization, denitrogenization,hydrogenation, alkylation, dealkylation, hydrodealkylation,transalkylation, cyclization, dehydrocyclization, cracking,hydrocracking, reforming, disproportionation, polymerization, and thelike processes. In particular, I have ascertained that a catalyst,comprising a combination of catalytically effective amounts of aplatinum group component, a lanthanide component, a Group IVA metalliccomponent and a halogen component with a porous refractory carriermaterial, can enable the performance of hydrocarbon conversion processesutilizing dualfunction catalysts to be substantially improved if themetallic components are uniformly dispersed throughout the carriermaterial in the hereinafter specified amounts and if their oxidationstates are controlled to be in the states hereinafter specified.Moreover, I have determined that an acidic catalytic composite,comprising a combination of catalytically effective amounts of aplatinum group component, a lanthanide compo nent, a Group IVA metalliccomponent and a chloride component with an alumina carrier material, canbe utilized to substantially improve the performance of a reformingprocess which operates on a low-octane gasoline fraction to produce ahigh-octane reformate if the metallic components are uniformlydistributed throughout the alumina carrier material in the properamounts and if their oxidation states are fixed in the stateshereinafter specified. In the case of a reforming process, the principaladvantage associated with the use of the novel catalyst of the presentinvention involves the acquisition of the capability to operate in astable manner in a high severity operation; for example, a low pressurereforming process designed to produce a high yield of C reformate havingan octane of about 100 F-l clear. As indicated, the present inventionessentially involves the finding that the addition of a Group IVAmetallic component and a lanthanide component to a dual-function acidichydrocarbon conversion catalyst containing a platinum group componentcan enable the performance characteristics of the resulting catalyst tobe sharply and materially improved, if the hereinafter specifiedlimitations on amounts of ingredients, oxidation states of metals anddistribution of metallic components in the support are met.

It is, accordingly, one object of the present invention to provide atrimetallic hydrocarbon conversion catalyst having superior performancecharacteristics when utilized in a hydrocarbon conversion process. Asecond object is to provide a trimetallic catalyst having dualfunctionhydrocarbon conversion performance characteristics that are relativelyinsensitive to the deposition of hydrocarbonaceous material thereon. Athird object is to provide preferred methods of preparation of thiscatalytic composite which insures the achievement and maintenance of itsproperties. Another object is to provide an improved reforming catalysthaving superior activity, selectivity and stability characteristics. Yetanother object is to provide a dual-function hydrocarbon conversioncatalyst which utilizes a combination of a Group IVA metallic componentand a lanthanide component to promote an acidic catalyst containing aplatinum or palladium or iridium metal component.

In brief summary, the present invention is, in one embodiment, acatalytic composite comprising a porous carrier material containing, onan elemental basis, about 0.01 to about 2 wt. platinum group metal,about 0.1 to about 3.5 wt. halogen, about 0.01 to about 5 wt. Group IVAmetal and a lanthanide element in an amount sufficient to result in anatomic ratio of lanthanide element to platinum group metal of about 0. 1:1 to about 1.25:1, wherein the platinum group metal, lanthanide elementand Group IVA metal are uniformly dispersed throughout the porouscarrier material, wherein substantially all of the platinum group metalis present in the elemental metallic state and wherein substantially allof the Group IVA metal and of the lanthanide element are present in anoxidation state above that of the corresponding elemental metal.

A second embodiment relates to a catalytic composite comprising a porouscarrier material containing, on an elemental basis, about 0.05 to about1 wt. platinum or palladium or iridium metal, about 0.5 to about 1.5 wt.halogen, about 0.05 to about 2 wt. Group IVA metal, and a lanthanideelement in an amount sufficient to result in an atomic ratio oflanthanide element to platinum or palladium or iridium of about 0.4: 1to about 1:1, wherein the platinum or palladium or iridium is present inthe corresponding elemental metallic state, wherein substantially all ofthe Group IVA metal is present in an oxidation state above that of theelemental metal and wherein substantially all of the lanthanide elementis present in an oxidation state above that of the correspondingelemental metal.

Another embodiment relates to a catalytic composite comprising acombination of the catalytic composite described in the first embodimentwith a sulfur component in an amount sufficient to incorporate about0.05 to about 0.5 wt. sulfur, calculated on an elemental basis.

Yet another embodiment relates to a process for the conversion ofhydrocarbon comprising contacting the hydrocarbon and hydrogen with thecatalytic composite described above in the first embodiment athydrocarbon conversion conditions.

A preferred embodiment relates to a process for reforming a gasolinefraction which comprises contacting the gasoline fraction and hydrogenwith the catalytic composite described above in the second embodiment atreforming conditions selected to produce a high-octane reformate.

Other objects and embodiments of the present invention relate toadditional details regarding preferred catalytic ingredients, preferredamounts of ingredients, suitable methods of composite preparation,operating conditions for use in the hydrocarbon conversion processes,and the like particulars which are hereinafter given in the followingdetailed discussion of each of these facets of the present invention.

The trimetallic catalyst of the present invention comprises a porouscarrier material or support having combined therewith catalyticallyeffective amounts of a platinum group component, a lanthanide component,a Group IVA metallic component, and a halogen component.

Considering first the porous carrier material utilized in the presentinvention, it is preferred that the material be a porous, adsorptive,high-surface area support having a surface area of about 25 to about 500m /g. The porous carrier material should be relatively refractory to theconditions utilized in the hydrocarbon converscope of the presentinvention carrier materials which have traditionally been utilized indual-function hydrocarbon conversion catalysts such as: (1) activatedcarbon, coke, or charcoal; (2) silica or silica gel, silicon carbide,clays and silicates including those synthetically-prepared andnaturally-occurring, which may or may not be acid treated, for example,attapulgus clay, china clay, diatomaceous earth, fullers earth, kaoline,kieselguhr, etc.; (3) ceramics, porcelain, crushed firebrick, bauxite;(4) refractory inorganic oxides such as alumina, titanium dioxide,zirconium dioxide, chromium oxide, zinc oxide, magnesia, thoria, boria,silicaalumina, silica-magnesia, chromia-alumina, aluminaboria,silica-zirconia, etc.; (5) crystalline zeolitic aluminosilicates such asnaturally-occurring or syntheticallyprepared mordenite and/or faujasite,either in the hydrogen form or in a form which has been treated withmulti-valent cations; (6) spinels such as MgAl O FeAl O ZnAl O,,, CaAlO, and other like compounds have the formula MO.Al O where M is a metalhaving a valence of 2; and (7) combinations of elements from one or moreof these groups. The preferred porous carrier materials for use in thepresent invention are refractory inorganic oxides, with best resultsobtained with an alumina carrier material. Suitable alumina materialsare the crystalline aluminas known as the gamma-, eta-, andtheta-alumina, with gammaor etaalumina giving best results. In addition,in some embodiments the alumina carrier material may contain minorproportions of other well known refractory inorganic oxides such assilica, zirconia, magnesia, etc.; however, the preferred support issubstantially pure gamma-, or eta-alumina. Preferred carrier materialshave an apparent bulk density of about 0.3 to about 0.7 g/cc and surfacearea characteristics such that the average pore diameter is about to 300Angstroms, the pore volume is about 0.1 to about 1 cc/g and the surfacearea is about 100 to about 500 m /g. In general, best results aretypically obtained with a gammaalumina carrier material which is used inthe form of shperical particles having: a relatively small diameter(i.e. typically about l/ 16 inch), an apparent bulk density of about 0.5to about 0.6 g/cc, a pore volume of about 0.4 cc/g, and a surface areaof about 175 m /g.

The preferred alumina carrier material may be prepared in any suitablemanner and may be synthetically prepared or natural occurring. Whatevertype of alumina is employed it may be activated prior to use by one ormore treatments including drying calcination, steaming, etc., and it maybe in a form known as activated alumina, activated alumina of commerce,porous alumina, alumina gel, etc. For example, the alumina carrier maybe prepared by adding a suitable alkaline reagent, such as ammoniumhydroxide to a salt of aluminum such as aluminum chloride, aluminumnitrate, etc., in an amount to form an aluminum hydroxide gel which upondrying and calcining is converted to alumina. The alumina carrier may beformed in any de sired shape such as spheres, pills, cakes, extrudates,powders, granules, tablets, etc., and utilized in any desired size. Forthe purpose of the present invention a particularly prefered form ofalumina is the sphere; and alumina spheres may be continuouslymanufactured by the well known oil drop method which comprises: formingan alumina hydrosol by any of the techniques taught in the art andpreferably by reacting aluminum metal with hyrochloric acid, combiningthe resulting hydrosol with a suitable gelling agent and dropping theresultant mixture into an oil bath maintained at elevated temperatures.The droplets of the mixture remain in the oil bath until they set andform hydrogel spheres. The spheres are then continuously withdrawn fromthe oil bath and typically subjected to specific aging treatments in oiland an ammoniacal solution to further improve their physicalcharacteristics. The resulting aged and gelled particles are then washedand dried at a relatively low temperature of about 300 F. to about 400F. and subjected to a calcination procedure at a temperature of about850 to about l,300 F. for a period of about 1 to about 20 hours. Thistreatment effects conversion of the alumina hydrogel to thecorresponding crystalline gamma-alumina. See the teachings of U.S. Pat.No. 2,620,314 for additional details.

One essential constituent of the instant multi-metallic catalyticcomposite is the Group IVA metallic component. By the use of the genericterm Group IVA metallic component it is intended to cover the metals ofGroup IVA of the Periodic Table. More specifically, it is intended tocover: germanium, tin, lead and mixtures of these metals. It is anessential feature of the present invention that substantially all of theGroup IVA metallic component is present in the final catalyst in anoxidation state above that of the elemental metal. In other words, thiscomponent may be present in chemical combination with one or more of theother ingredients of the composite, or as a chemical compound of theGroup IVA metal such as the oxide, sulfide, halide, oxyhalide,oxychloride, aluminate, and the like compounds. Based on the evidencecurrently available, it is believed that best results are obtained whensubstantially all of the Group IVA metallic component exists in thefinal composite in the form of the corresponding oxide such as the tinoxide, germanium oxide, and lead oxide, and the subsequently describedoxidation and reduction steps, that are preferably used in thepreparation of the instant composite, are believed to result in acatalytic composite which contains an oxide of the Group IVA metalliccomponent. Regardless of the state in which this component exists in thecomposite, it can be utilized therein in any amount which iscatalytically effective, with the preferred amount being about 0.01 toabout 5 wt. thereof, calculated on an elemental basis and the mostpreferred amount being about 0.05 to about 2 wt. The exact amountselected within this broad range is preferably determined as a functionof the particular Group IVA metal that is utilized. For instance, in thecase where this component is lead, it is preferred to select the amountof this component from the low end of this range namely, about 0.01 toabout 1 wt. Additionally, it is preferred to select the amount of leadas a function of the amount of the platinum group component as explainedhereinafter. In the case where this component is tin, it is preferred toselect from a relatively broader range of about 0.05 to about 2 wt.thereof. And, in the preferred case, where this component is germaniumthe selection can be made from the full breadth of the stated rangespecifically, about 0.01 to about 5 wt. with best results at about 0.05to about 2 wt.

This Group IVA component may be incorporated in the composite in anysuitable manner known to the art to result in a uniform dispersion ofthe Group IVA moiety throughout the carrier material such as,coprecipitation or cogellation with the porous carrier material, ionexchange with the carrier material, or impregnation of the carriermaterial at any stage in its preparation. It is to be noted that it isintended to include within the scope of the present invention allconventional procedures for incorporating a metallic component in acatalytic composite, and the particular method of incorporation used isnot deemed to be an essential feature of the present invention so longas the Group IVA component is uniformly distributed throughout theporous carrier material. One acceptable method of incorporating theGroup IVA component into the catalytic composite involves cogelling theGroup IVA component during the preparation of the preferred carriermaterial, alumina. This method typically involves the addition of asuitable soluble compound of the Group IVA metal of interest to thealumina hydrosol. The resulting mixture is then commingled with asuitable gelling agent, such as a relatively weak alkaline reagent, andthe resulting mixture is thereafter preferably gelled by dropping into ahot oil bath as explained hereinbefore. After aging, drying andcalcining the resulting particles there is obtained an intimatecombination of the oxide of the Group IVA metal and alumina. Onepreferred method of incorporating this component into the compositeinvolves utilization of a soluble decomposable compound of theparticular Group IVA metal of inter est to impregnate the porous carriermaterial either before, during or after the carrier material iscalcined. In general, the solvent used during this impregnation step isselected on the basis of its capability to dissolve the desired GroupIVA compound without affecting the porous carrier material which is tobe impregnated; or dinarily, good results are obtained when water is thesolvent; thus the preferred Group IVA compounds for use in thisimpregnation step are typically water-soluble and decomposable. Examplesof suitable Group IVA compounds are: germanium difluoride, germaniumtetralkoxide, germanium dioxide, germanium tetrafluoride, germaniummonosulfide, tin chloride, tin bromide, tin dibromide di-iodide, tindichloride di-iodide, tin chromate, tin difluoride, tin tetrafluoride,tin tetraiodide, tin sulfate, tin tartrate, lead acetate, lead bromate,lead bromide, lead chlorate, lead chloride, lead citrate, lead formate,lead lactate, lead malate, lead nitrate, lead nitrite, lead dithionate,and the like compounds. In the case where the Group IVA component isgermanium, a preferred impregnation solution is germanium tetrachloridedissolved in anhydrous alcohol. In the case of tin, tin chloridedissolved in water is preferred. In the case of lead, lead nitratedissolved in water is preferred. Regardless of which impregnationsolution is utilized, the Group IVA component can be impregnated eitherprior to, simultaneously with, or after the other metallic componentsare added to the carrier material. Ordinarily, best results are obtainedwhen this component is impregnated simultaneously with the othermetallic components of the composite. Likewise, best results areordinarily obtained when the Group IVA component is germanium oxide ortin oxide.

Regardless of which Group IVA compound is used in the preferredimpregnation step, it is essential that the Group IVA metallic componentbe uniformly distributed throughout the carrier material. In order toachieve this objective when this component in incorporated byimpregnation, it is necessary to maintain the pH of the impregnationsolution at a relatively low level corresponding to about 7 to about 1or less and to dilute the impregnation solution to a volume which is atleast approximately the same or greater than the volume of the carriermaterial which is impregnated. It is preferred to use a volume ratio ofimpregnation solution to carrier material of at least 1:1 and preferablyabout 2:1 to about 10:1 or more. Similarly, it is preferred to use arelatively long contact time during the impregnation step ranging fromabout one-fourth hour up to about one-half hour or more before drying toremove excess solvent in order to insure a high dispersion of the GroupIVA metallic component in the carrier material. The carrier material is,likewise, preferably constantly agitated during this preferredimpregnation step.

A second essential ingredient of the subject catalyst is the platinumgroup component. That is, it is intended to cover the use of platinum orpalladium or iridium or rhodium or osmium or ruthenium or mixturesthereof as a second component of the present composite. It is anessential feature of the present invention that substantially all of theplatinum group component exists within the final catalytic composite inthe elemental metallic state (i.e. as elemental platinum or palladium oriridium etc.). Generally the amount of the second component used in thefinal composite is relatively small compared to the amount of the othercomponents combined therewith. In fact, the platinum group componentgenerally will comprise about 0.01 to about 2 wt. of the final catalyticcomposite, calculated on an elemental basis. Excellent results areobtained when the catalyst contains about 0.05 to about 1 wt. ofplatinum, iridium or palladium metal.

This platinum group component may be incorporated in the catalyticcomposite in any suitable manner known to result in a relatively uniformdistribution of this component in the carrier material such ascoprecipitation or cogellation, ion-exchange, or impregnation. Thepreferred method of preparing the catalyst involves the utilization of asoluble, decomposable compound of a platinum group metal to impregnatethe carrier material in a relatively uniform manner. For example, thiscomponent may be added to the support by commingling the latter with anaqueous solution of chloroplatinic, chloroiridic or chloropalladic acid.Other water-soluble compounds of platinum group metals may be employedin impregnation solutions and include ammonium chloroplatinate,bromoplatinic acid, platinum dichloride, platinum tetrachloride hydrate,platinum dichlorocarbonyl dichloride, dinitrodiaminoplatinum, tetramineplatinum chloride, palladium chloride, palladium nitrate, palladiumsulfate, etc. The utilization of a platinum group metal chloridecompound, such as chloroplatinic, chloroiridic or chloropalladic acid,is preferred since it facilitates the incorporation of both the platinumgroup component and at least a minor quantity of the halogen componentin a single step. Hydrogen chloride or the like acid is also generallyadded to the impregnation solution in order to further facilitate theincorporation of the halogen component and the uniform distribution ofthe metallic component throughout the carrier material. In addition, itis generally preferred to impregnate the carrier material after it hasbeen calcined in order to minimize the rise of washing away the valuableplatinum or palladium compounds; however, in some cases it may beadvantageous to impregnate the carrier material when it is in a gelledstate.

Yet another essential ingredient of the present catalytic composite is alanthanide component. By the use of the generic expression lanthanidecomponent" it is intended to cover the 15 elements and mixtures thereofthat are commonly known as the lanthanide series or rare earths.Specifically, included within this definition are the followingelements: lanthanum, cerium, praseodymium, neodymium, promethium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium and lutetium. This component may be present in theinstant trimetallic composite in any form wherein substantially all ofthe lanthanide element is present in an oxidation state above that ofthe corresponding metal such as in chemical combination with one or moreof the other ingredients of the composite, or as a chemical compoundsuch as a lan thanide oxide, sulfide, halide, oxychloride, aluminate,and the like. However, best results are believed to be obtained whensubstantially all of the lanthanide component exists in the form of thecorresponding oxide and the subsequently described oxidation andprereduction procedure is believed, on the basis of the availableevidence, to result in this condition. This lanthanide component may beutilized in the composite in any amount which is catalyticallyeffective, with the preferred amount being about 0.01 to about 1 wt.thereof, calculated on an elemental lanthanide basis. Typically bestresults are obtained with about 0.05 to about 0.5 wt. lanthanideelement. According to the present invention, it is essential to selectthe specific amount of lanthanide element from within this broad weightrange as a function of the amount of the platinum group component, on anatomic basis, as is explained hereinafter. The lanthanide elements thatare especially preferred for purposes of the present invention arelanthanum, cerium, and neodymium with neodymium giving best results.

The lanthanide component may be incorporated into the catalyticcomposite in any suitable manner known to those skilled in the catalystformulation art which ultimately results in a uniform dispersion of thelanthanide moiety in the carrier material. In addition, it may be addedat any stage of the preparation of the composite either duringpreparation of the carrier material or thereafter and the precise methodof incorporation used is not deemed to be critical. However, bestresults are obtained when the lanthanide component is incorporated in amanner such that it is relatively uniformly distributed throughout thecarrier material in a positive oxidation state or a state which iseasily converted to a positive oxidation state in the subsequentlydescribed oxidation step. One preferred procedure for incorporating thiscomponent into the composite involves cogelling or coprecipitating thelanthanide component during the preparation of the preferred carriermaterial, alumina. This procedure usually comprehends the addition of asoluble, decomposable compound of a lanthanide element such as neodymiumnitrate to the alumina hydrosol before it is gelled. The resultingmixture is then finished by conventional gelling, aging, drying andcalcination steps as explained hereinbefore. Another preferred way ofincorporating this component is an impregnation step wherein the porouscarrier material is impregnated with a suitable lanthanidecompound-containing solution either before, during or after the carriermaterial is calcined. Preferred impregnation solutions are aqueoussolutions of watersoluble, decomposable lanthanide compounds such as alanthanide acetate, a lanthanide bromide, a lanthanide perchlorate, alanthanide chloride, a lanthanide iodide, a lanthanide nitrate, and thelike compounds. Best results are ordinarily obtained when theimpregnation solution is an aqueous solution of a lanthanide chloride ora lanthanide nitrate. This lanthanide component can be added to thecarrier material, either prior to, simultaneously with, or after theother metallic components are combined therewith. Best results areusually achieved when this component is added simultaneously with theother metallic components. In fact, excellent results have beenobtained, as reported in the examples, with a one step impregnationprocedure using an aqueous solution comprising the desired amounts ofchloroplatinic acid, a lanthanide nitrate, hydrochloric acid and asuitable compound of the desired Group IVA metal.

It is essential to incorporate a halogen component into the trimetalliccatalytic composite of the present invention. Although the precise formof the chemistry of the association of the halogen component with thecarrier material is not entirely known, it is customary in the art torefer to the halogen component as being com bined with the carriermaterial, or with the other ingredients of the catalyst in the form ofthe halide (e.g. as the chloride). This combined halogen may be eitherfluorine, chlorine, bromine, or mixtures thereof. Of these fluorine and,particularly, chloride are preferred for the purpose of the presentinvention. The halogen may be added to the carrier material in anysuitable manner, either during preparation of the support or before orafter the addition of the other components. For example, the halogen maybe added, at any stage of the preparation of the carrier material or tothe calcined carrier material, as an aqueous solution of a suitable,decomposable halogen-containing compound such as hydrogen fluoride,hydrogen chloride, hydrogen bromide, ammonium chloride, etc. The halogencomponent or a portion thereof, may be combined with the carriermaterial during the impregnation of the latter with the metalliccomponents; for example, through the utilization of a mixture ofchloroplatinic acid and hydrogen chloride. In another situation, thealumina hydrosol which is typically utilized to form the preferredalumina carrier material may contain halogen and thus contribute atleast a portion of the halogen component to the final composite. Forreforming, the halogen will be typically combined with the carriermaterial in an amount sufficient to result in a final composite thatcontains about 0.1 to about 3.5%, and preferably about 0.5 to about 1.5%by weight of halogen calculated on an elemental basis. In isomerizationor hydrocracking embodiments, it is generally preferred to utilizerelatively larger amounts of halogen in the catalyst typically, rangingup to about 10 wt. halogen calculated on an elemental basis, and morepreferably about 1 to about 5 wt.

Regarding the preferred amounts of the various metallic components ofthe subject catalyst, I have found it to be an essential practice tospecify the amounts of the lanthanide component as a function of theamount of the platinum group component. On this basis, the amount of thelanthanide component is selected so that the atomic ratio of lanthanideelement to the platinum group metal contained in the composite is about0.111 to 1.25:1 with best results obtained when the range is about 0.4:1to about 1:1. Similarly, it is a preferred practice to select the amountof the Group IVA metallic component to produce a composite containing anatomic ratio of Group IVA metal to platinum group metal within the broadrange of about 0.05:1 to 10:1. However, for the Group IVA metal toplatinum group metal ratio, the best practice is to select this ratio onthe basis of the following preferred ranges for the individual Group IVAspecies: (1) for germanium, it is about 0.3:1 to :1, with the mostpreferred range being about 0.611 to about 6.1; (2) for tin, it is about0.121 to 3:1, with the most preferred range being about 0.5:1 to 1.511;and, (3) for lead, it is about 0.05:1 to 0.9: l with the most preferredrange being about 0.1:1 to 0.75:1.

Another significant parameter for the present catalyst is the totalmetals content which is defined to be the sum of the platinum groupcomponent, the lanthanide component, and the Group IVA metallic compo- Ynent, calculated on an elemental basis. Good results are ordinarilyobtained with the subject catalyst when this parameter is fixed at avalue of about 0.15 to about 2.5 wt. 7c, with best results ordinarilyachieved at a metals loading of about 0.3 to about 2 wt.

In embodiments of the present invention wherein the instant trimetalliccatalytic composite is used for dehydrogenation of dehydrogenatablehydrocarbons or for the hydrogenation of hydrogenatable hydrocarbons, itis ordinarily a preferred practice to include an alkali or alkalineearth metal component in the composite and to maintain the halogencomponent at the lowest possible value. More precisely, this optionalcomponent is selected from the group consisting of the compounds of thealkali metals cesium, rubidium, potassium, sodium and lithium and thecompounds of the alkaline earth metals calcium, strontium, barium andmagnesium. Generally, good results are obtained in these embodimentswhen this component constitutes about 0.1 to about 5 wt. 70 of thecomposite, calculated on an elemental basis. This optional alkali oralkaline earth metal component can be incorporated in the composite inany of the known ways, with impregnation with an aqueous solution of asuitable water-soluble, decomposable compound being preferred.

An optional ingredient for the trimetallic catalyst of the presentinvention is a Friedel-Crafts metal halide component. This ingredient isparticularly useful in bydrocarbon conversion embodiments of the presentin vention wherein it is preferred that the catalyst utilized has astrong acid or cracking function associated therewith for example, anembodiment wherein hydrocarbons are to be hydrocracked or isomerizedwith the catalyst of the present invention. Suitable metal halides ofthe Friedel-Crafts type include aluminum chloride, aluminum bromide,ferric chloride, ferric bromide, zinc chloride, and the like compounds,with the aluminum halides and particularly aluminum chloride ordinarilyyielding best results. Generally, this optional in gredient can beincorporated into the composite of the present invention by any of theconventional methods for adding metallic halides of this type; however,best results are ordinarily obtained when the metallic halide issublimed onto the surface of the carrier material according to thepreferred method disclosed in U.S. Pat. No. 2,999,074. The component cangenerally be utilized in any amount which is catalytically effective,with a value selected from the range of about 1 to about 100 wt. of thecarrier material generally being preferred.

Regardless of the details of how the components of the catalyst arecombined with the porous carrier material, the final catalyst generallywill be dried at a temperature of about 200 to about 600 F. for a periodof at least about 2 to 24 hours or more, and finally calined 12 oroxidized at a temperature of about 700 F. to about 1 F. in an airatmosphere for a period of about 0.5 to about 10 hours in order toconvert substantially all of the metallic components to thecorresponding oxide forms. Because a halogen component is utilized inthe catalyst, best results are generally obtained when the halogencontent of the catalyst is adjusted during the calcination step byincluding a halogen or a halogencontaining compound in the airatmosphere utilized. In particular, when the halogen component of thecatalyst is combined chloride, it is preferred to use a mole ratio of H0 to HCl of about 5:1 to about 100:1 during at least a portion of thecalcination step in order to adjust the final chloride content of thecatalyst to a range of about 0.1 to about 3.5 wt.

It is an essential feature of the present invention that the resultantoxidized trimetallic catalytic composite is subjected to a substantiallywater-free reduction step prior to its use in the conversion ofhydrocarbons. This step is designed to insure a uniform and finelydivided dispersion of the metallic components throughout the carriermaterial and to selectively reduce the platinum group component to thecorresponding metal while maintaining substantially all of the Group IVAmetallic component and the lanthanide component in positive oxidationstates. Preferably, substantially pure and dry hydrogen (i.e. less than20 vol. ppm. H O) is used as the reducing agent in this step. Thereducing agent is contacted with the oxidized catalyst at conditionsincluding a temperature of about 800 to about 1200 F. and a period oftime of about 0.5 to 2 hours effective to reduce substantially all ofthe platinum group component to the elemental metallic state whilemaintaining substantially all of the Group IVA metallic component andthe lanthanide component in oxidation states above that of thecorresponding elemental metals. This reduction treatment may beperformed in situ as part of a start-up sequence if precautions aretaken to predry the plant to a substantially water-free state and ifsubstantially water-free hydrogen is used.

The resulting reduced catalytic composite may, in some cases, bebeneficially subjected to a presulfiding operation designed toincorporate in the catalytic composite from about 0.05 to about 0.5 wt.sulfur calculated on an elemental basis. Preferably, this presulfidingtreatment takes place in the presence of hydrogen and a suitablesulfur-containing and metallic sulfide producing compound such ashydrogen sulfide, lower molecular weight mercaptans, organic sulfides,disulfides, etc. Typically, this procedure comprises treating theselectively reduced catalyst with a sulfiding gas such as a mixture ofhydrogen and hydrogen sulfide having about 10 moles of hydrogen per moleof hydrogen sulfide at conditions sufficient to effect the desiredincorporation of sulfur, generally including a temperature ranging fromabout 50 up to about 1100 F. or more. It is generally a good practice toperform this presulfiding step under substantially water-freeconditions.

According to the present invention, a hydrocarbon charge stock andhydrogen are contacted with a trimetallic catalyst of the type describedabove in a hydrocarbon conversion zone. This contacting may beaccomplished by using the catalyst in a fixed bed system, a moving bedsystem, a fluidized bed system, or in a batch type operation; however,in view of the danger of 'attrition losses of the valuable catalyst andof well known operational advantages, it is preferred to use a 13 fixedbed system. In this system, a hydrogen-rich gas and the charge stock arepreheated by any suitable heating means to the desired reactiontemperature and then are passed, into a conversion zone containing afixed bed of the catalyst type previously characterized. It is, ofcourse, understood that the conversion zone may be one or more separatereactors with suitable means therebetween to insure that the desiredconversion temperature is maintained at the entrance to each reactor. Itis also important to note that the reactants may be contacted with thecatalyst bed in either upward, downward, or radical flow fashion withthe latter being preferred. In addition, the reactants may be in theliquid phase, a mixed liquid-vapor phase, or a vapor phase when theycontact the catalyst, with best results obtained in the vapor phase.

In the case where the trimetallic catalyst of the present invention isused in a reforming operation, the reforming system will comprise areforming zone containing a fixed bed of the catalyst type previouslycharacterized. This reforming zone may be one or more separate reactorswith suitable heating means therebetween to compensate for theendothermic nature of the reactions that take place in each catalystbed. The hydrocarbon feed stream that is charged to this reformingsystem will comprise hydrocarbon fractions containingnaphthenes andparaffins that boil within the gasoline range. The preferred chargestocks are those consisting essentially of naphthenes and paraffins,although in some cases aromatics and/or olefins may also be present.This preferred class includes straight run gasolines, natural gasolines,synthetic gasolines and the like. On the other hand, it is frequentlyadvantageous to change thermally or catalytically cracked gasolines orhigher boiling fractions thereof. Mixtures of straight run and crackedgasolines can also be used to advantage. The gasoline charge stock maybe a full boiling gasoline having an initial boiling point of from about50 to about 150 F. and an end boiling point within the range of fromabout 325 to about 425 F., or may be a selected fraction thereof whichgenerally will be a higher boiling fraction commonly referred to as aheavy naphtha for example, a naphtha boiling in the range of C to 400 F.In some cases, it is also advantageous to charge pure hydrocarbons ormixtures of hydrocarbons that have been extracted from hydrocarbondistillates for example, straight-chain paraffins which are to beconverted to aromatics. It is preferred that these charge stocks betreated by conventional catalytic pretreatment methods such ashydrorefining, hydrotreating, hydrodesulfurization, etc., to removesubstantially all sulfurous, nitrogenous and water-yielding contaminantstherefrom and to saturate any olefins that may be contained therein.

In other hydrocarbon conversion embodiments, the charge stock will be ofthe conventional type customarily used for the particular kind ofhydrocarbon conversion being effected. For example, in a typicalisomerization embodiment the charge stock can be a paraffinic stock richin C to C normal paraffins, or a normal butane-rich stock, or ann-hexane-rich stock, or a mixture of xylene isomers, etc. In adehydrogenation embodiment, the charge stock can be any of the knowndehydrogenatable hydrocarbons such as an aliphatic compound containing 2to 30 carbon atoms per molecule, a C to C normal paraffin, a C to Calkylaromatic, a naphthene and the like. In hydrocracking embodiments,the charge stock will be typically a gas oil, heavy cracked cycle oil,etc. In addition alkylaromatic and naphthenes can be convenientlyisomerized by using the catalyst of the present invention. Likewise,pure hydrocarbons or substantially pure hydrocarbons can be converted tomore valuable products by using the trimetallic catalyst of the presentinvention in any of the hydrocarbon conversion processes, known to theart, that use a dual-function catalyst.

In a reforming embodiment, it is generally preferred to utilize thenovel trimetallic catalytic composite in a substantially water-freeenvironment. Essential to the achievement of this condition in thereforming zone is the control of the water level present in the chargestock and the hydrogen stream which is being charged to the zone. Bestresults are ordinarily obtained when the total amount of water enteringthe conversion zone from any source is held to a level less than 50 ppm.and preferably less than 20 ppm.; expressed as weight of equivalentwater in the charge stock. In general, this can be accomplished bycareful control of the water present in the charge stock and in thehydrogen stream. The charge stock can be dried by using any suitabledrying means known to the art such as a conventional solid adsorbenthaving a high selectivity for water; for instance, sodium or calciumcrystalline aluminosilicates, silica gel, activated alumina, molecularsieves, anhydrous calcium sulfate, high surface area sodium and the likeadsorbents. Similarly, the water content of the charge stock may beadjusted by suitable stripping operations in a fractionation column orlike device. And in some cases, a combination of adsorbent drying anddistillation drying may be used advantageously to effect almost completeremoval of water from the charge stock. Preferably, the charge stock isdried to a level corresponding to less than 20 ppm. of H 0 equivalent.In general, it is preferred to maintain the hydrogen stream entering thehydrocarbon conversion zone at a level of about 10 vol. ppm. of water orless. In the case where the water content of hydrogen stream is abovethis range, this can be conveniently accomplished by contacting thehydrogen stream with a suitable desiccant such as those mentioned aboveat conventional drying conditions.

In the reforming embodiment, an effluent stream is withdrawn from thereforming zone and passed through a cooling means to a separation zone,typically maintained at about 25 to 150 F., wherein a hydrogen-rich gasis separated from a high octane liquid product, commonly called anunstabilized reformate. When a super-dry operation is desired, at leasta portion of this hydrogen-rich gas is withdrawn from the separatingzone and passed through an adsorption zone containing an adsorbentselective for water. The resultant substantially water-free hydrogenstream can then be recycled through suitable compressing means back tothe reforming zone. The liquid phase from the separating zone istypically withdrawn and commonly treated in a fractionating system inorder to adjust the butane concentration, thereby controlling frontendvolatility of the resulting reformate.

The conditions utilized in the numerous hydrocarbon conversionembodiments of the present invention are those customarily used in theart for the particular reaction, or combination of reactions, that is tobe effected. For instance, alkylaromatics and paraffin isom erizationconditions include: a temperature of about 32 to about 100 F. andpreferably about to about 600 F.; a pressure of atmospheric to aboutatmospheres; a hydrogen to hydrocarbon mole ratio of about 0.511 toabout 20:1 and a LHSV (calculated on the basis of equivalent liquidvolume of the charge stock contacted with the catalyst per hour dividedby the volume of conversion zone containing catalyst) of about 0.2 hr.to hr. Dehydrogenation conditions include: a temperature of about 700 toabout l,250 F., a pressure of about 0.1 to about 10 atmospheres, aliquid hourly space velocity of about 1 to 40 hr. and a hydrogen tohydrocarbon mole ratio of about 1:1 to 20:1. Likewise, typicallyhydrocracking conditions include: a pressure of about 500 psig. to about3,000 psig.; a temperature of about 400 to about 900 F.; a LI-ISV ofabout 0.1 hr. to about 10 hr.; and hydrogen circulation rates of about1,000 to 10,000 SCF per barrel of charge.

In the reforming embodiment of the present invention the pressureutilized is selected from the range of about 0 psig. to about 1,000psig., with the preferred pressure being about 50 psig. to about 600psig. Partic ularly good results are obtained at low pressure; namely, apressure of about 50 to 350 psig. In fact, it is a singular advantage ofthe present invention that it allows stable operation at lower pressurethan have heretofore been successfully utilized in so-called continuousreforming systems (i.e. reforming for periods of about to about 200 ormore barrels of charge per pound of catalyst without regeneration) withall platinummonometallic catalysts. In other words, the trimetalliccatalyst of the present invention allows the operation of a continuousreforming system to be conducted at low pressure (i.e. 100 to about 350psig.) for about the same or better catalyst life before regeneration ashas been heretofore realized with conventional monometallic catalysts athigher pressures (i.e. 400 to 600 psig.). On the other hand, thestability feature of the present invention enables reforming operationconducted at pressures of 400 to 600 psig. to achieve substantiallyincreased catalyst life before regeneration.

Similarly, the temperature required for reforming is generally lowerthan that required for a similar reforming operation using a highquality catalyst of the prior art. This significant and desirablefeature of the present invention is a consequence of the selectivity ofthe trimetallic catalyst of the present invention for theoctane-upgrading reactions that are preferably induced in a typicalreforming operation. Hence, the present invention requires a temperaturein the range of from about 800 to about 1 100 F. and preferably about900 to about 1050 F. As is well known to those skilled in the continuousreforming art, the initial selection of the temperature within thisbroad range is made primarily as a function of the desired octane of theproduct reformate considering the characteristics of the charge stockand of the catalyst. Ordinarily, the temperature then is thereafterslowly increased during the run to compensate for the inevitabledeactivation that occurs to provide a constant octane product.Therefore, it is a feature of the present invention that the rate atwhich the temperature is increased in order to maintain a constantoctane product, is substantially lower for the catalyst of the presentinvention than for a high quality reforming catalyst which ismanufactured in exactly the same manner as the catalyst of the presentinvention except for the inclusion of the lanthanide and Group IVAmetallic components. Moreover, for the catalyst of the presentinvention, the C yield loss for a given temperature increase issubstantially lower than for a 16 high quality reforming catalyst of theprior art. In addition, hydrogen production is substantially higher.

The reforming embodiment of the present invention also typicallyutilizes sufficient hydrogen to provide an amount of about 1 to about 20moles of hydrogen per mole of hydrocarbon entering the reforming zone,with excellent results being obtained when about 5 to about 10 moles ofhydrogen are used per mole of hydrocar bon. Likewise, the liquid hourlyspace velocity (LI-ISV) used in reforming is selected from the range ofabout 0.1 to about 10 hr., with a value in the range of about 1 to about5 hr? being preferred. In fact, it is a feature of the present inventionthat it allows operations to be conducted at higher LHSV than normallycan be stably achieved in a continuous reforming process with a highquality reforming catalyst of the prior art. This last feature is ofimmense economic significance because it allows a continuous reformingprocess to operate at the same throughput level with less catalystinventory than that heretofore used with conventional reformingcatalysts at no sacrific in catalyst life before regeneration.

The following working examples are given to illustrate further thepreparation of the trimetallic catalytic composite of the presentinvention and the use thereof in the conversion of hydrocarbons. It isunderstood that the examples are intended to be illustrative rather thanrestrictive.

EXAMPLE I This example demonstrates a particularly good method ofpreparing the trimetallic catalytic composite of the present invention.

A tin-containing alumina carrier material comprising 1/16 inch sphereswas prepared by: forming an alumi num hydroxyl chloride sol bydissolving substantially pure aluminum pellets in a hydrochloric acidsolution, adding stannic chloride to the resulting sol in an amountselected to result in a finished catalyst containing about 0.5 wt. tin,adding hexamethylenetetramine to the resulting tin-containing aluminasol, gelling the resulting solution by dropping it into an oil bath toform spherical particles of an aluminumand tin-containing hydrogel,aging and washing the resulting particles and finally drying andcalcining the aged and washed particles to form spherical particles ofgammaalumina containing a uniform dispersion of about 0.5 wt. tin in theform of tin oxide and about 0.3 wt. combined chloride. Additionaldetails so to this method of preparing the preferred gamma-aluminacarrier material are given in the teachings of US. Pat. No. 2,620,314.

An aqueous impregnation solution containing chloroplatinic acid,neodymium nitrate and hydrogen chloride was then prepared. Thetin-containing alumina carrier material was thereafter admixed with theimpregnation solution. The amount of reagents contained in thisimpregnation solution was calculated to result in a final compositecontaining, on an elemental basis, 0.47 wt. platinum, 0.26 wt. neodymiumand 0.5 wt. tin. In order to insure uniform dispersion of the metalliccomponents throughout the carrier material, the amount of hydrochloricacid used was about 3 wt. of the alumina particles. This impregnationstep was performed by adding the carrier material particles to theimpregnation mixture with constant agitation. In addition, the volume ofthe solution was approximately the same as the volume of the carriermaterial particles.

The impregnation mixture was maintained in contact with the carriermaterial particles for a period of about one-half hour at a temperatureof about 70 F. Thereafter, the temperature of the impregnation mixturewas raised to about 225 F. and the excess solution was evaporated in aperiod of about 1 hour. The resulting dried particles were thensubjected to a calcination or oxidation treatment in an air atmosphereat a temperature of about 975 F. for about 1 hour. This oxidation stepwas designated to convert substantially all of the metallic ingredientsto the corresponding oxide forms. The calcined spheres were thencontacted with an air stream containing H and I-ICl in a mole ratio ofabout 30:1 for about 4 hours at 975 F. in order to adjust the halogencontent of the catalyst particles to a value of about 1.05 wt.

The resulting catalyst particles were analyzed and found to contain, onan elemental basis, about 0.47 wt. platinum, about 0.26 wt. neodymium,about 0.5 wt. tin and about 1.05 wt. chloride. For this catalyst, theatomic ratio of tin to platinum is 1.75:1 and the atomic ratio ofneodymium to platinum is 0.75:1.

Thereafter, the catalyst particles were subjected to a dry pre-reductiontreatment, designed to reduce the platinum component to the elementalstate while maintaining the tin and neodymium components in positiveoxidation states, by contacting them for 1 hour with a substantiallypure hydrogen stream containing less than 5 vol. ppm. H O at atemperature of about 1,050 F., a pressure slightly above atmospheric,and a flow rate of the hydrogen stream through the catalyst particlescorresponding to a gas hourly space velocity of about 720 hr.. Theresulting catalyst is hereinafter referred to as catalyst A.

EXAMPLE II In order to compare the novel trimetallic catalytic compositeof the present invention with a leading bimetallic catalytic compositeof the prior art in a manner calculated to bring out the beneficialinteraction between the lanthanide component and a platinumandtin-containing catalyst, a comparison test was made between thetrimetallic catalyst of the present invention which was prepared inExample I (i.e. catalyst A) and a superior bimetallic reforming catalystof the prior art which contained a combination of platinum and tin asits hydrogenation-dehydrogenation component. The control catalyst was acombination of a platinum component, a tin component and a chloridecomponent with a gamma-alumina carrier material in an amount sufficientto result in the final catalyst containing about 0.6 wt. platinum, about0.5 wt. tin and about 1.05 wt. chloride. The control catalyst ishereinafter referred to as catalyst B. Catalyst B was prepared by amethod identical to that set forth in Example I except for the inclusionof the lanthanide element and the increase in the platinum componentfrom 0.47 wt. to 0.6 wt.

These catalysts were then separately subjected to a high stressaccelerated catalytic reforming evaluation charge stock was utilized andits pertinent characteris-' tics are set forth in Table I. It is to benoted that in both cases the test was conducted under substantiallywaterfree conditions with the only significant source of water being the5 wt. ppm. present in the charge stock. Like- 18 wise, it is to beobserved that both runs were performed under substantially sulfur-freeconditions with the only sulfur input into the plant being the 0.1 wt.sulfur contained in the charge stock.

TABLE I Analysis of Charge Stock Aromatics, vol. 7:

This accelerated reforming test was specifically designed to determinein a very short period of time whether the catalyst being evaluated hassuperior characteristics for use in a high severity reforming operation.Each run consisted of a series of evaluation periods of 24 hours each,each of these periods comprised a 12 hour line-out period followed by a12 hour test period during which the C product reformate from the plantwas collected and analyzed. Both test runs were performed at identicalconditions which comprised a liquid hourly spaced velocity (Ll-ISV) of2.0 hrf, a pressure of 100 psig., a 5:1 gas to oil ratio, and an inletreactor temperature which was continuously adjusted throughout the testin order to achieve and maintain a C target octane of 102 F-l clear.

Both tests were performed in a pilot plant scale reforming unitcomprising a reactor containing the catalyst undergoing evaluation, ahydrogen separation zone, a dubutanizer column and suitable heatingmeans, pumping means, condensing means comprising means and the likeconventional equipment. The flow scheme utilized in this plant includescommingling a hydrogen recycle stream with the charge stock and heatingthe resulting mixture to the desired conversion temperature. The heatedmixture is then passed downflow into a reactor containing the catalystundergoing evaluation as a stationary bed. An effluent stream is thenwithdrawn from the bottom of the reactor, cooled to about F. and passedto a gas-liquid separation zone wherein a hydrogen-rich gaseous phaseseparates from a liquid hydrocarbon phase. A portion of the gaseousphase is then continuously passed through a high surface area sodiumscrubber and the resulting substantially water-free and sulfur-freehydrogen stream is returned to the reactor in order to supply thehydrogen recycle stream. The'excess gaseous phase from the separationzone is recovered as the hydrogen-containing product stream (commonlycalled excess recycle gas). The liquid phase from the separation zone iswithdrawn therefrom and passed to a debutanizer column wherein lightends(i.e. C to C are taken overhead as debutanizer gas and'a C reformatestream recovered as the principal bottom product.

The results of the separate tests performed on the particularlypreferred catalyst of the present invention,

Catalyst A, and the control catalyst, Catalyst B, are presented for eachtest period in Table ll in terms of inlet temperature to the reactor inF. necessary to achieve the target octane level, the amount of Creformate recovered expresseed as vol. of the charge stock, and thepurity of the recycle gas expressed as mole hydrogen contained in same.These results are shown in Table II as a function of time expressed inbarrels of charge processed per pound of catalyst in the reactor (BPP).

TABLE ll Results of Accelerated Reforming Test CATALYST A CATALYST B" T,BPP T, "F (2 wt.'7( H 7: T, "F C wt.7r H ,7(

Referring now to the results of the comparison test presented in Table11, it is evident that the effect of the lanthanide element on theplatinum and tin bimetallic catalyst is to substantially promote sameand to enable a catalyst containing less platinum to outperform acatalyst containing a substantially greater amount of platinum in theareas of activity, selectivity and stability. That is, the datapresented in Table 11 clearly indicates that the trimetallic catalyst ofthe present invention is markedly superior to the control catalyst in ahigh severity reforming process. As was pointed out in detailhereinbefore, a good measure of activity for a reforming catalyst is theinlet temperature in the reactor which is required to make target octaneand the data presented in Table 11 on this variable clearly shows thatcatalyst A was significantly more active than catalyst B; for example,at, a time corresponding to 1.5 barrels of charge per pound of catalyst,catalyst A required a re actor inlet temperature of 1,004 F. in order tomake octane which stands in sharp contrast to the 1,01 3 F. requirementof catalyst B at the same point in the run. This 9 F. difference intemperature requirement for octane is conclusive evidence of the abilityof the catalyst of the present invention to materially accelerate therate of the involved reforming reaction in view of the well known ruleof thumb that the rate of reaction doubles with every 10 C. charge inreactor temperature. Thus the data clearly shows that the composite ofthe present invention was materially more active than the controlcatalyst. However, activity is only one of the necessary characteristicsneeded in order for a catalyst to demonstrate superiority. Activitycharacteristics must be coupled with superior selectivity and stabilitycharacteristics in order to demonstrate improved performance.Selectivity is measured directly by C yield and the data presented inTable II clearly indicates that catalyst A consistently produced betteryields than catalyst B. (It is to be noted that the dashes in Table I1represent periods where the relevant analyses of the product streamswere not made.) Another indication of good selectivity characteristicsis the hydrogen content of the excess recycle gas and on this basis thecatalyst of the present invention exhibited hydrogen purity which wereanalogous to those observed for catalyst B. On the other hand, goodstability characteristics are shown by the rate of change of theactivity It is intended to cover by the following claims, all changesand modifications of the above disclosure of the present invention whichwould be self-evident to a man of ordinary skill in the hydrocarbonconversion art or the catalyst formulation art.

I claim as my invention:

1. A process for converting a hydrocarbon which comprises contacting thehydrocarbon at hydrocarbon conversion conditions with a catalyticcomposite comprising a porous carrier material containing, on anelemental basis, about 0.01 to about 2 wt. platinum group metal, about0.01 to about 5 wt. germanium, about 0.1 to about 3.5 wt. halogen, and alanthanide series component in an amount sufficient to result in anatomic ratio of lanthanide series component to platinum group metal ofabout 0.1:1 to about 1.25:1, wherein the platinum group metal, germaniumand lanthanide series component are uniformly dispersed throughout theporous carrier material, wherein substantially all of the platinum groupmetal is present in the elemental metallic state, wherein substantiallyall of the germanium is present in an oxidation state above that of thecorresponding elemental metal and wherein substantially all of thelanthanide series component is present in an oxidation state above thatof the corresponding elemental metal.

2. A process as defined in claim 1 wherein the platinum group metal isplatinum.

3. A process as defined in claim 1 wherein the platinum group metal ispalladium.

4. A process as defined in claim 1 wherein the platinum group metal isiridium.

5. A process as defined in claim 1 wherein the halogen component iscombined chloride.

6. A process as defined in claim 1 wherein the porous carrier materialis a refractory inorganic oxide.

7. A process as defined in claim 6 wherein the refractory inorganicoxide is alumina.

8. A process as defined in claim 1 wherein the lanthanide seriescomponent is neodymium.

9. A process as defined in claim 1 wherein the lanthanide seriescomponent is cerium.

10. A process as defined in claim 1 wherein the lan- .thanide seriescomponent is lanthanum.

21 composite in an amount sufficient to result in an atomic ratio oflanthanide series component to platinum group metal of about 0.4:1 toabout 1:1.

12. A process as defined in claim 1 wherein the catalytic compositecontains about 0.05 to about 0.5 wt. sulfur, calculated on an elementalbasis.

13. A process as defined in claim 1 wherein substantially all of thegermanium metal is present in the catalytic composite as the oxide.

14. A process as defined in claim 1 wherein substantially all of thelanthanide series component is present in the catalytic composite in theform of the corresponding oxide.

15. A process as defined in claim 1 wherein the atomic ratio ofgermanium metal to platinum group metal contained in the composite isabout 0.05:1 to about :1.

16. A process as defined in claim 1 wherein the catalytic compositecontains about 0.05 to about 1 wt. platinum group metal, about 0.05 toabout 2 wt. Group IVA metal, 0.5 to about 1.5 wt. halogen and an atomicratio of lanthanide series component to platinum group metal of about0.4:1 to about 1:1.

17. A process as defined in claim 1 wherein the contacting of thehydrocarbon with the catalytic composite is performed in the presence ofhydrogen.

18. A process as defined in claim 1 wherein the type of hydrocarbonconversion is catalytic reforming of a gasoline fraction to produce ahigh-octane reformate, wherein the hydrocarbon is contained in thegasoline fraction, wherein the contacting is performed in the presenceof hydrogen and wherein the hydrocarbon conversion conditions arereforming conditions.

19. A process as defined in claim 18 wherein the reforming conditionsinclude a temperature of about 800 to 1 F., a pressure of about 0 toabout 1000 psig., a liquid hourly space velocity of about 0.1 to about10 hr. and a mole ratio of hydrogen to hydrocarbon of about 1:1 to about20:1.

20. A process as defined in claim 18 wherein the contacting step isperformed in a substantially water-free environment.

21. A process as defined in claim 18 wherein the reforming conditionsinclude a pressure of about 50 to about 350 psig.

1. A PROCESS FOR CONVERTING A HYDROCARBON WHICH COMPRISES CONTACTING THE HYDROCARBON AT HYDROCARBON CONVERSATION CONDITIONS WITH A CATALYTIC COMPOSITION COMPRISING A POROUS CARRIER MATERIAL CONTAINING, ON AN ELEMENT BASIS, ABOUT 0.001 TO ABOUT 2 WT. % PLANTINUM GROUP METAL, ABOUT 0.01 TO ABOUT 5 WT. % GERMATIUM, ABOUT 0.1 TO ABOUT 3.5 WT. % HALOGEN, AND A LANTHANIDE SERIES COMPONENT IN AN AMOUNT SUFFICIENT TO RESULT IN AN ATOMIC RATIO OF LANTHANISE SERIES COMPONENT TO PLANTINUM GROUP METAL OF ABOUT 0.1 : 1 TO ABOUT 1.25:1, WHEREIN THE PLATINUM GROUP METAL, GERMANIUM AND LANTHANIDE SERIES COMPONENT ARE UNIFORMLY DISPERSED TROUGHOUT THE POROUS CARRIER MATERIAL, WHEREIN SUBSTANTIALLY ALL OF THE PLANTINUM GROUP METAL IS PRESENT IN THE ELEMENTAL METALLIC STATE, WHEREIN SUBSTANTIALLY ALL OF THE GERMANIUM IS PRESENT IN AN OXIDATION STATE ABOVE THAT OF THE CORRESPONDING ELEMENTAL METAL AND WHEREIN SUBSTANTIALLY ALL OF THE LANTHANIDE SERIES COMPONENT IS PRESENT IN AN OXIDATION STATE ABOVE THAT OF THE CORRESPONDING ELEMENTAL METAL.
 2. A process as defined in claim 1 wherein the platinum group metal is platinum.
 3. A process as defined in claim 1 wherein the platinum group metal is palladium.
 4. A process as defined in claim 1 wherein the platinum group metal is iridium.
 5. A process as defined in claim 1 wherein the halogen component is combined chloride.
 6. A process as defined in claim 1 wherein the porous carrier material is a refractory inorganic oxide.
 7. A process as defined in claim 6 wherein the refractory inorganic oxide is alumina.
 8. A process as defined in claim 1 wherein the lanthanide series component is neodymium.
 9. A process as defined in claim 1 wherein the lanthanide series component is cerium.
 10. A process as defined in claim 1 wherein the lanthanide series component is lanthanum.
 11. A process as defined in claim 1 wherein the lanthanide series component is present in the catalytic composite in an amount sufficient to result in an atomic ratio of lanthanide series component to platinum group metal of about 0.4:1 to about 1:1.
 12. A process as defined in claim 1 wherein the catalytic composite contains about 0.05 to about 0.5 wt. % sulfur, calculated on an elemental basis.
 13. A process as defined in claim 1 wherein substanTially all of the germanium metal is present in the catalytic composite as the oxide.
 14. A process as defined in claim 1 wherein substantially all of the lanthanide series component is present in the catalytic composite in the form of the corresponding oxide.
 15. A process as defined in claim 1 wherein the atomic ratio of germanium metal to platinum group metal contained in the composite is about 0.05:1 to about 10:1.
 16. A process as defined in claim 1 wherein the catalytic composite contains about 0.05 to about 1 wt. % platinum group metal, about 0.05 to about 2 wt. % Group IVA metal, 0.5 to about 1.5 wt. % halogen and an atomic ratio of lanthanide series component to platinum group metal of about 0.4:1 to about 1:1.
 17. A process as defined in claim 1 wherein the contacting of the hydrocarbon with the catalytic composite is performed in the presence of hydrogen.
 18. A process as defined in claim 1 wherein the type of hydrocarbon conversion is catalytic reforming of a gasoline fraction to produce a high-octane reformate, wherein the hydrocarbon is contained in the gasoline fraction, wherein the contacting is performed in the presence of hydrogen and wherein the hydrocarbon conversion conditions are reforming conditions.
 19. A process as defined in claim 18 wherein the reforming conditions include a temperature of about 800* to 1100* F., a pressure of about 0 to about 1000 psig., a liquid hourly space velocity of about 0.1 to about 10 hr. 1 and a mole ratio of hydrogen to hydrocarbon of about 1:1 to about 20:1.
 20. A process as defined in claim 18 wherein the contacting step is performed in a substantially water-free environment.
 21. A process as defined in claim 18 wherein the reforming conditions include a pressure of about 50 to about 350 psig. 